WO2011069331A1 - 锂离子电池 - Google Patents

锂离子电池 Download PDF

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Publication number
WO2011069331A1
WO2011069331A1 PCT/CN2010/001974 CN2010001974W WO2011069331A1 WO 2011069331 A1 WO2011069331 A1 WO 2011069331A1 CN 2010001974 W CN2010001974 W CN 2010001974W WO 2011069331 A1 WO2011069331 A1 WO 2011069331A1
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Prior art keywords
lithium ion
ion battery
battery according
lithium
inorganic
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PCT/CN2010/001974
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English (en)
French (fr)
Inventor
李翔
唐杰
孙庆津
徐晟�
罗建海
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Microvast Power Systems Huzhou Co Ltd
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Microvast Power Systems Huzhou Co Ltd
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Priority to US13/514,973 priority Critical patent/US9281540B2/en
Publication of WO2011069331A1 publication Critical patent/WO2011069331A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of lithium ion batteries and similar storage technologies, and more particularly to a lithium ion battery comprising an ion selective conduction layer.
  • Lithium-ion batteries have the advantages of high weight and volume energy density, long cycle life, a certain degree of safety and reliability, and the ability to perform rapid charge and discharge. In recent years, they have become a hot spot in the research and development of new energy storage technologies. High energy and high power applications are popular.
  • a typical lithium ion secondary battery is composed of a positive and negative electrode material, an electrolyte, a separator, and a battery casing packaging material.
  • a polymer lithium ion battery refers to a lithium ion battery in which an electrolyte uses a solid polymer electrolyte (SPE).
  • the battery is compounded by a positive current collector, a positive electrode film, a solid polymer electrolyte membrane, a negative electrode membrane, and a negative current collector, and the outer package is an aluminum-plastic composite film, and the edges thereof are heat-sealed to obtain a polymer lithium ion battery.
  • Existing solid polymer electrolyte membrane is doped with a proportion of inorganic particles such as Si0 2, A1 2 0 3 and LiCF 3 S0 3 directly as a polymer film such as an electrolyte, typically a polymer with a polyethylene oxide Alkene PE0, etc., such electrolytes generally have a thickness of more than 100 Mm, and lithium ions in the electrolyte can move in the molecular chain.
  • the copper ions oxidized as a current collector metal such as copper foil can pass through the solid polymer electrolyte membrane relatively smoothly. Once the battery is over-discharged, the copper foil is easily oxidized, so that a large amount of copper ions can be smoothly performed.
  • Chinese Patent C '2922234 discloses an over-discharge protection circuit for a power lithium-ion battery, comprising a pair of input and output ports and a battery unit, a port at the pair of input and output ports and an electrode of the battery unit Interconnecting a discharge control switch, wherein the battery unit is formed by connecting a plurality of lithium ion rechargeable batteries in series; and further comprising an overdischarge voltage detecting unit that compares a voltage of the battery with a set voltage and outputs a comparison result, according to which Output of discharge voltage detecting unit The signal controls an overdischarge logic control unit that turns on/off the discharge control switch.
  • the overdischarge protection circuit can automatically disconnect the circuit and stop the discharge, so that any one of the batteries will not Damaged by over-discharge, ensuring safe discharge of the battery unit.
  • Cia patent Q 101404406 discloses a lithium battery protection circuit: the protection circuit is composed of an overcharge control tube, an overdischarge control tube and a protection IC, and the overcharge control tube and the overdischarge control tube are monitored by the protection IC and controlled.
  • the protection IC is a CMOS integrated circuit block, which includes an overcharge protection circuit, an overdischarge protection circuit and an overcurrent protection circuit.
  • the protection IC is provided between the output negative V- and the gate of the MOS transistor connected to the output negative V-.
  • Chinese patent CN101159375 discloses a lithium battery power supply control protection circuit and a control and protection method. The method described above controls the battery power supply to prevent overdischarge by detecting the battery voltage, and can completely shut down the battery through software.
  • the purpose of preventing excessive discharge of the lithium ion battery is achieved by an external circuit design, and the damage to the battery caused by the problem of excessive discharge of the lithium ion battery cannot be eliminated in essence or from the inside of the battery.
  • High-capacity battery packs or battery pack systems often consist of thousands or even tens of thousands of single cells. This external circuit protection design is difficult to protect single cells, and the reliability of the circuit is difficult to guarantee, and the management cost. Higher.
  • the technical problem to be solved by the present invention is that the prior art cannot substantially eliminate the excessive discharge of the lithium ion battery inside the battery to cause damage to the battery itself.
  • the metal used for the anode current collector in most cases, copper metal
  • the discharge is negative, the negative electrode is oxidized and loses electrons.
  • the overdischarge occurs, the lithium ion of the negative electrode will migrate to the positive electrode according to equation (1).
  • the copper metal of the current collector will follow the equation ( The form of 2) is oxidized, and copper ions generated by oxidation of copper will migrate toward the positive electrode and precipitate on the surface of the positive electrode material or on the separator.
  • the technical solution provided by the present invention is: adding a conductive layer having preferential selective conduction to lithium ions between the positive electrode and the negative electrode of the lithium ion battery, and the selective conductive layer has a comparative layer A good lithium ion pass rate, while at the same time, the battery is over-discharged to cause a metal ion generated by the current collector of the negative electrode to have a blocking effect.
  • the lithium ion battery claimed in the present invention comprises a positive electrode, a negative electrode and an electrolyte system, and an ion selective conductive layer is further included between the positive electrode and the negative electrode, and the ion selective conductive layer is composed of a high molecular polymer and an inorganic having lithium ion conductivity.
  • the electrolyte system may be an organic electrolyte system.
  • the organic electrolyte is at least one of LiPF 6 , LiAsFa, LiC10 4 or LiBF 4 as an electrolyte, and at least one of EC, PC, EPC, BC; DME, DMC, EMC, DEC or DMF is An organic solution prepared by solvent.
  • the active material on the positive electrode includes at least one of commonly used, commercially available LiCoO 2 , LiNiO 2 Li n 2 0 4 > 6?0 4 or other composite oxide.
  • the negative electrode includes a current collector made of any one of copper, nickel, aluminum, and stainless steel alloy.
  • the active material on the negative electrode includes any of the existing negative electrode materials, especially carbonaceous materials or materials containing lithium titanate.
  • the area of the ion selective conductive layer is preferably not less than the area of the negative electrode, such that the ion selective conductive layer can completely isolate the negative electrode from the positive electrode and completely prevent conduction of electrons between the positive electrode and the negative electrode inside the battery.
  • the commonly used separators in commercial lithium-ion batteries are mostly porous membranes, and there are lithium ions directly penetrating both sides of the membrane. Physical through hole.
  • the ion selective conductive layer in the lithium ion battery claimed in the present invention is dense, and lithium ions cannot directly penetrate the conductive layer.
  • the ion selective conductive layer described in the present invention has the function that lithium ions can exchange lithium ions with an inorganic lithium salt having lithium ion conductivity, thereby realizing lithium ion conduction, thereby effectively preventing generation of a current current collector after being oxidized. The passage of other metal ions.
  • the inorganic lithium salt having lithium ion conductivity include Li 0 7, LiB0 2, Li 4 Si0 4, Li 2 Se0 4, Li 2 Zr0 3, Li, Li 2 Ti0 3, Li 2 Te0 3, Li 2 Ta0 3, LiA10 2, Li 3 As0 4, a -LiAlSiA in any one of, or a mixture of any two or wherein preferably Li 2 B 4 0 7, Li 2 Zr0 3 , Li 2 Ti0 3 , Li 4 SiQ ⁇ , LiA10 2 , 1 ⁇ 80 2 or . - ⁇ At least one of eight 18 0 6 .
  • M in the inorganic lithium salt Li 0 x according to the present invention includes the element P, wherein M may include at least one of B, Si, C, Al, Ti or Zr in addition to P.
  • the inorganic lithium salt having lithium ion conductivity particularly preferably includes Li 3 P0 4 .
  • the ion selective conductive layer may be a dense film formed by a high molecular polymer and an inorganic lithium salt having lithium ion conductivity, and there is no simultaneous penetration between the two sides of the film. Physical through hole.
  • the inorganic lithium salt is uniformly dispersed in the high molecular polymer.
  • the high molecular polymer includes PAN' (polyacrylonitrile), P MA (polymethyl methacrylate), PVDF (polyvinylidene fluoride) or PVC (polyvinyl chloride), PVDF-HFP (polyimide) At least one of vinyl fluoride-hexafluoropropylene), PVDF-CTFE (polyvinylidene fluoride-trichloroethylene), PS (polysulfone) or PES (polyethersulfone).
  • Copolymers or homopolymers comprising PVDF are preferred; and PVDF copolymers include PVDF HFP, PVDF The homopolymer consists of PVDF.
  • This dense film can be attached to the porous film inside the existing battery, and the dense film of the present invention is bonded to at least one side of the porous film.
  • This dense film can also be used independently, such as directly as a battery separator or attached to the positive and negative surfaces of the battery.
  • the ion selective conductive layer may further be a thin layer composed of an inorganic lithium salt covering at least one surface of the positive electrode and the negative electrode.
  • the lithium ion battery claimed in the present invention has the ability to prevent internal short circuit of the battery and to increase the cycle life of the battery when it is over-discharged or subjected to abnormal reverse charging.
  • the ion selective conductive layer contained therein has a good lithium ion conducting function, and has a barrier effect on the metal ions generated after the negative current collector is oxidized.
  • the ion selective conductive layer is between the negative electrode and the electrolyte, for example, covering the surface of the negative electrode material, the lithium "dendritic" phenomenon caused by charging or overcharging of the lithium ion battery can be effectively prevented, thereby preventing the battery Internal short circuit.
  • Fig. 1 is a flow chart showing a process for preparing an ion-selective conductive film comprising Li 3 P0 4 of the present invention.
  • Example 2 is a SEM photograph of a porous structural surface of an ion-selective conductive film containing 1 ⁇ 3 ?0 4 prepared in Example 1 of the present invention.
  • 3 is a SEM photograph of a dense surface of an ion-selective conductive film containing 1 ⁇ 4 4 prepared in Example 1 of the present invention.
  • Example 4 is a SEM photograph of a cross section of an ion-selective conductive film containing 1 ⁇ 3 ?0 4 prepared in Example 1 of the present invention.
  • Fig. 5 is an XRD chart showing the surface of a positive electrode material after disassembly of a battery made of a Celgard 2320 separator in Example 4 of the present invention.
  • Fig. 6 is an XRD chart showing the surface of a positive electrode material after disassembly of a lithium ion battery manufactured in Example 3 of the present invention.
  • Fig. 7 is an XRD chart showing the surface of a lithium ion battery film produced in Example 3 of the present invention.
  • Figure 8 is an AC impedance map of different separators in Example 2 of the present invention.
  • the pulverization method may include ball milling, sanding, airflow pulverizing, ultrafine pulverizing grinding, etc.;
  • the obtained slurry system is cast into a film by a casting machine, and the thickness is 5 ⁇ 50 after drying.
  • the film forming process is a mature casting process, and the apparent structure of the film is as follows:
  • the other side is a smoother and dense structure.
  • the non-smooth side may make the film itself have good wettability with the electrolyte, so that the film resistance can be effectively reduced.
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene
  • the obtained slurry was filtered and defoamed, and cast into a film on a carrier film having a smooth surface using a film casting machine, and dried to obtain a dense film having a film thickness of 20 ⁇ m.
  • the side of the dense film and the carrier film is smooth and dense, and the other side is a matte structure.
  • the surface of the separator was analyzed by scanning electron microscopy (SEM), as shown in Fig. 2. It can be seen from the figure that the surface is not smooth; as shown in Fig. 3, the surface of the separator is etched. It is relatively smooth and dense;
  • Figure 4 shows the cross-sectional structure of the Li 3 P0 4 ion selective conductive film.
  • Test method The membrane was clamped between standard gaskets with a 1.0 mm square hole through a gas permeability tester with a small hole in the center of the gasket to allow gas to flow through, under a steady pressure, a certain measurement The volume of gas (100 cc) required to flow through a sample of a specific area. Using the ion selective conductive membrane containing Li 3 P0 4 prepared above as a test, 100 cc of gas still failed to flow for 30 minutes. The same test was carried out using a commercial Celgard 2320 diaphragm, and 100 cc of gas was completely flowed in 350-450 seconds.
  • the ion selective conductive film containing 1 ⁇ 4 4 prepared in Example 1 and the Celgard 2320 separator (both thicknesses of 20 Mm) were used in the electrolyte (LiPF 6 /EC-DEC, the volume ratio of EC to DEC was 1 : 1 ) Fully soaked, the diaphragm was sandwiched between two blocking electrodes made of two stainless steel sheets in an Ar atmosphere glove box, and an AC impedance measurement was performed using an electrochemical workstation at room temperature. The measured data is shown in Fig. 8.
  • the solid line represents the AC impedance curve including the Li 3 P0 ion selective conductive film
  • the broken line represents the AC impedance curve of the Celgard 2320 diaphragm, from which it can be seen that:
  • Example 1 The dense film has a lower pure resistance than the Celgard 2320 separator, and the lithium ion conductivity is higher.
  • Preparation of positive electrode According to the ratio, the positive electrode active material lithium iron phosphate (LiFeP0, 87 W t%, conductive carbon black 5 W t%, binder polyvinylidene fluoride PVDF 8 wt%), evenly dispersed in N-A
  • the positive electrode active material lithium iron phosphate (LiFeP0, 87 W t%, conductive carbon black 5 W t%, binder polyvinylidene fluoride PVDF 8 wt%), evenly dispersed in N-A
  • MP bis-2-pyrrolidone
  • the negative active material (charcoal powder 92 wt%, conductive carbon black 2 wt%, binder polyfluoride
  • the olefin PVDF is 6 wt%) uniformly dispersed in the X-methyl-2-pyrrolidine I (XP) solution to prepare a mixed slurry of the negative electrode, and the slurry is coated on the negative current collector copper foil. After the dry roll was pressed, a negative electrode tab was obtained.
  • Example 3 A lithium ion battery fabricated in Example 3 and a lithium ion battery fabricated using a Celgard 2320 separator were subjected to a comparative test:
  • the two sets of batteries subjected to reverse polarity charging were disassembled separately, and the surface of the positive electrode material of the battery made of Celgard 2320 diaphragm was subjected to XRD test, and the XRD pattern showed clear peaks of copper metal XRD (as shown in Fig. 5).
  • the battery prepared in Example 3 was free from metallic copper on the surface of the positive electrode material of the disassembled battery, and no peak of copper metal appeared on the surface of the positive electrode material by XRD (Fig. 6).
  • the XRD test on the diaphragm also showed no peaks of copper metal (as shown in Figure 7), and the same fabricated battery could continue to charge and discharge after the reverse polarity charging.
  • Example 3 A lithium ion battery fabricated in Example 3 and a lithium ion battery fabricated using a Celgard 2320 separator were subjected to a comparative test:
  • the discharge voltage of the two sets of lithium-ion batteries was reduced from the usual 2. 5 V voltage to 1. 0 V and 0.1 V, and the battery cycle performance test was performed with a discharge current of 0.5 C.
  • the lithium ion battery fabricated in Example 3 can still work normally after 30 overdischarge cycles, and the lithium ion battery fabricated using the Celgard 2320 separator exhibits significant capacity degradation after 10 times of the same overdischarge cycle. Basically, normal charging and discharging cannot be performed.
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene
  • the obtained slurry was filtered and defoamed, and a film casting machine was used to cast a film on the surface of a positive electrode sheet of a lithium ion battery, and after drying, a dense positive electrode electrode piece was obtained, and the thickness was 20 Mm. After drying and rolling, it can be made into a lithium ion battery with a negative electrode of a lithium ion battery and an electrolyte, and no additional separator is needed.
  • the obtained slurry was filtered and defoamed, and a film casting machine was used to cast a film on the surface of a lithium ion battery negative electrode sheet which was formed into a film, and dried to obtain a dense film having a thickness of 20 ⁇ . After drying and rolling, it can be made into a lithium ion battery with a positive electrode of a lithium ion battery and an electrolyte, and no additional separator is needed.
  • 5 g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) was dissolved in a mixed solvent of 149.2 g of acetone and 200 g of 1-methyl-2-pyrrolidinium (NMP), and stirred until the mixture was dispersed.
  • the vinyl fluoride was completely dissolved, and then 78. 6 g of lithium phosphate powder was added, and the mixture was ground and dispersed until a uniform slurry was obtained.
  • the obtained slurry was filtered and defoamed, and a film casting machine was used to strictly control the distance between the cutter head and the carrier tape, and the film was cast on a smooth carrier film to provide a film thickness of 5 Wn.
  • the above-mentioned film having a thickness of 5 Mm is subjected to hot press lamination with a conventional physical through-hole film widely used in a lithium ion battery, and the pressing temperature is controlled to 120 V, and the pressure is 0.35 kg/cm 2 , which is obtained by including 1 ⁇ 0 4 .
  • the inorganic lithium salt having lithium ion conductivity in the ion selective conductive layer in the above embodiment is not limited to Li 3 P0 4 , and may be Li 3 P0 4 doped with B, Si, C. Al, Ti. Or a compound of any one or two of Zr.
  • the inorganic lithium salt having lithium ion conductivity may also be Li 2 B 4 0 7 , Li 2 ZrO 3 , Li 2 W0., Li 2 TiO 3 , Li 2 TeO Lija 0 3 , Li 2 Se0 4 , Li 4 SiO.
  • LiA10 2 , LiF, LiB0 2 , Li 3 As0 4 or a - LiAlSi 2 0 6 because they contain lithium ions as compared with Li 3 P0 4 and due to their crystal structure characteristics and The crystal defects after doping enable lithium ion exchange and conduction functions.
  • the high molecular polymer includes at least one of PAN or PVC in addition to PVDF.
  • PVDF-HFP is preferred because PVDF-HFP has good chemical stability in the electrolyte and PVDF as a binder in the lithium ion battery electrode, so the PVDF polymer material has a very high capacity in a lithium ion battery. Good chemical compatibility.

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Description

锂离子电池
技术领域
本发明涉及锂离子电池及类似储电技术领域， 尤其是一种包含离子选择性传导层的锂离 子电池。
背景技术
锂离子电池具有重量及体积能量密度高、循环寿命长， 具备一定程度的安全性及可靠性， 并且能够进行快速充放电等优点， 近年来己成为新型储电技术研究和幵发的热点， 在大能量 和高功率应用领域备受欢迎。 通常的锂离子二次电池由正、 负极材料、 电解液、 隔膜以及电 池外壳包装材料组成。
聚合物锂离子电池是指电解质使用固态聚合物电解质（SPE)的锂离子电池。 电池由正极 集流体、 正极膜、 固态聚合物电解质膜、 负极膜、 负极集流体复合成型， 外包封包装为铝塑 复合薄膜， 并将其边缘热熔封合， 得到聚合物锂离子电池。 现有的固体聚合物电解质膜是将 掺有一定比例的无机盐颗粒如 Si02、 A1203和 LiCF3S03等的聚合物薄膜直接作为电解质， 代表 性的聚合物有聚环氧乙烷 PE0等， 这类电解质厚度一般在 100 Mm以上， 电解质中的锂离子可 以在分子链中进行移动。 同时， 做为电流集流体金属比如铜箔氧化后的铜离子也可以比较顺 利的通过固体聚合物电解质膜， 一旦电池过度放电现象发生时， 容易造成铜箔氧化， 从而使 大量的铜离子能够顺利的迁移到正极材料表面； 另外这种固体电解质聚合物薄膜的主要缺点 是离子电导率较低， 常温下大约在 10— 5 S/cm左右， 比使用 LiPF6为电解质的液态电解液的电 导率小了 2个数量级左右。
锂离子电池作为动力电池使用时， 因为电压和容量需求， 往往需要将多节单体电池进行 串联、 并联使用， 以达到用电设备所需的工作电压和容量。 当实际连接于负载时， 由于电池 的固有一致性差异， 在电池管理系统管理状况及技术手段不完善时， 部分单体电池可能处于 过度放电状态， 过度放电将造成锂离子从负极的过度脱嵌及负极集流体 （通常为金属， 如铜 箔等） 被氧化等现象发生， 同时， 集流体产生的金属离子将会通过现有在锂离子电池中广泛 使用的物理贯穿孔薄膜 （如美国 Celgard公司， 日本 UBE公司生产的物理贯穿孔薄膜） 到达 正极， 这样的结果， 将造成电池不可逆循环发生， 同时可能伴随电极间短路等现象， 结果是 影响电池的循环寿命和电池容量， 同时可能造成很大的安全隐患。
中国专利 C '2922234 公开了一种动力锂离子电池的过放电保护电路，它包括一对输入输 出端口和电池单元，在所述一对输入输出端口的一个端口和所述电池单元的一个电极之间连 接放电控制开关，所述电池单元由多节锂离子充电电池串联而成；它还包括可将电池的电压与 设定电压进行比较并输出比较结果的过放电电压检测部，根据所述过放电电压检测部的输出 信号控制所述放电控制开关通 /断的过放电逻辑控制部。当任何一节电池的电压低于设定的放 电限制电压或电池组的电压低于设定电压时，该过放电保护电路能自动断开电路，停止放电， 从而使任何一节电池都不会受到过放电的损坏，保证了电池单元的放电安全。
中国专利 Q 101404406公开了一种锂电池保护电路：该保护电路由过充电控制管、 过放电 控制管和保护 IC组成，过充电控制管和过放电控制管由保护 IC监视电池电压并进行控制,保 护 IC为 CMOS集成电路块,其中包括过充电保护电路,过放电保护电路和过电流保护电路，保护 IC中，在输出负极 V-和与输出负极 V-连接的 M0S晶体管的栅极之间设有钳位电路,在输出负 极 V-的电压在较大范围内变化时，钳位电路承受大部分的负压，使得 M0S晶体管的栅极承受电 压限制在 -2. 5V以内，并且不影响所述过充电保护电路，过放电保护电路和过电流保护电路的 功能。
中国专利 CN101159375公开了一种锂电池供电控制保护电路及控制保护方法， 所述的方 法通过对电池电压的检测，控制电池的供电，防止过放电，并且可以通过软件彻底关断电池。
上述的现有技术中， 都是通过外部的电路设计来达到防止锂离子电池过度放电的目的， 无法从本质上或者从电池内部消除锂离子电池过度放电问题对电池造成的损害。 高容量电池 包或电池组系统往往由几千甚至数万个的单体电池组成， 这种外部电路保护的设计很难做到 对单体电池的保护， 而且电路的可靠性难以保证， 管理成本较高。
发明内容
本发明所要解决的技术问题： 现有技术无法在电池内部从本质上消除锂离子电池过度放 电造成电池自身的损害。
现有的锂离子电池在放电完毕后强制继续放电 （过度放电） 或者反向充电的情况下， 会 在正极或者隔膜上析出负极集流体使用的金属（大多数情况为铜金属）， 其原因是： 放电时负 极被氧化失去电子， 当过度放电现象发生时， 负极的锂离子将根据方程式（1 )全部迁移到正 极， 当负极的锂离子完全脱嵌后， 集流体的铜金属将按照方程式（2 ) 的形式被氧化， 铜被氧 化生成的铜离子将向正极迁移， 并在正极材料表面或隔膜上析出。
Li „ ― LiT -f xe" (1)
Cu → Cu T ÷ 2e ( 2 )
因此， 为了解决上述的技术问题， 本发明提供的技术方案是： 在锂离子电池的正极与负 极之间增加一层对锂离子具有优先选择性传导的传导层， 这层选择性传导层具有较好的锂离 子通过率， 同时对电池过度放电导致负极的电流集流体产生的金属离子具有阻隔作用。
本发明所要求保护的锂离子电池， 包括正极、 负极、 电解质体系， 正极与负极之间还包 括离子选择性传导层，该离子选择性传导层由高分子聚合物和具有锂离子传导性的无机锂盐、 或者由具有锂离子传导性的无机锂盐组成， 所述的无机锂盐包括 Li Λ, 其中， m、 π的数值 保证 LiJ„0x为电中性， M选自 B、 P、 Si、 Se、 Zr、 W、 Ti、 Te、 Ta、 Al或 As中的至少一种。
所述的电解质体系可以为有机电解液体系。优选的有机电解液是以 LiPF6、 LiAsFa, LiC104 或者 LiBF4中的至少一种为电解质， 以 EC、 PC、 EPC、 BC；、 DME、 DMC、 EMC, DEC或者 DMF中的 至少一种为溶剂配制成的有机溶液。
所述正极上的活性材料包括常用的、 已经商品化的 LiCo02、 LiNi02 Li n204> 6?04或 者其它复合氧化物中的至少一种。
所述负极包括铜、 镍、 铝、 不锈钢合金中任意一种金属制成的电流集流体。
负极上的活性材料包括现有商品化的所有负极材料的任何一种， 尤其是含碳材料或者含 钛酸锂的材料。
所述离子选择性传导层的面积优选不小于负极的面积， 这样离子选择性传导层可以将负 极与正极完全隔离， 并且完全阻止电池内部正极和负极之间电子的传导。
现有商业化锂离子电池中普遍使用的隔膜 （比如由美国 Celgard公司或者日本 UBE公司 制造和提供的 PP/PE物理贯穿孔薄膜） 大多为多孔膜， 且存在可供锂离子直接穿透隔膜两面 的物理贯穿孔。 而本发明所要求保护的锂离子电池中的离子选择性传导层是致密的， 锂离子 不能直接穿透传导层。 本发明所描述的离子选择性传导层， 其功能为锂离子可以与具有锂离 子传导性的无机锂盐进行锂离子交换， 从而实现锂离子传导， 因此可以有效防止电流集流体 被氧化后所产生的其它金属离子的通过。
本发明所要求保护的锂离子电池， 所述的具有锂离子传导性的无机锂盐包括 Li 07、 LiB02、 Li4Si04、 Li2Se04、 Li2Zr03、 Li 、 Li2Ti03、 Li2Te03、 Li2Ta03、 LiA102、 Li3As04、 a -LiAlSiA 中的任何一种、 或者其中任意两种以上的混合物， 优选 Li2B407、 Li2Zr03、 Li2Ti03、 Li4SiQ〗、 LiA102、 1^802或。 -^八18 06中的至少一种。
本发明所述的无机锂盐 Li 0x中的 M包括元素 P， 其中， M除了包括 P， 还可以包括 B、 Si、 C、 Al、 Ti或 Zr中的至少一种。
具有锂离子传导性的无机锂盐特别优选包括 Li3P04。
本发明所要求保护的锂离子电池， 所述的离子选择性传导层可以为高分子聚合物和具有 锂离子传导性的无机锂盐共同制成的致密薄膜， 而且薄膜两面之间没有同时贯穿的物理贯穿 孔。 优选无机锂盐是均匀分散在高分子聚合物中的。 所述的高分子聚合物包括 PAN' (聚丙烯 腈）、 P MA (聚甲基丙烯酸甲酯）、 PVDF (聚偏二氟乙烯）或者 PVC (聚氯乙烯）、 PVDF-HFP (聚 偏二氟乙烯-六氟丙烯）、 PVDF-CTFE (聚偏二氟乙烯-三氯乙烯）、 PS (聚砜）或 PES (聚醚砜） 中的至少一种。 优选包括 PVDF的共聚物或者均聚物； 而 PVDF的共聚物包括 PVDF HFP, PVDF 的均聚物则由 PVDF 组成。 这层致密薄膜可贴合在现有电池内部的多孔膜上， 在多孔膜的至 少一侧有贴合有本发明所述的致密膜。 这层致密薄膜也可以独立使用， 比如直接作为电池的 隔膜或者贴合在电池正、 负极表面上。
本发明所要求保护的锂离子电池， 所述的离子选择性传导层还可以是覆盖在正极、 负极 的至少一个表面上的、 由无机锂盐组成的薄层。 本发明要求保护的锂离子电池在过度放电或者受到不正常反向充电时具有防止电池内部 短路的能力及增长电池循环寿命的能力。 其中包含的离子选择性传导层具有较好的锂离子传 导功能， 对于负极电流集流体被氧化后所产生的金属离子具有阻隔作用。 同时， 如果离子选 择性传导层在负极和电解液之间， 比如覆盖在负极材料的表面， 则能够有效的防止锂离子电 池在充电或过度充电所产生的锂 "枝晶"现象， 从而防止电池内部短路。
附图说明
图 1是本发明的包含 Li3P04的离子选择性传导膜的制备方法流程图。
图 2是本发明实施例 1制备的包含 1^3?04的离子选择性传导膜的多孔结构面的 SEM照片。 图 3是本发明实施例 1制备的包含 1^^04的离子选择性传导膜的致密面 SEM照片。
图 4是本发明实施例 1制备的包含 1^3?04的离子选择性传导膜的断面的 SEM照片。
图 5是本发明实施例 4中用 Celgard 2320隔膜制成的电池拆卸后正极材料表面的 XRD图。 图 6是本发明实施例 3制做的锂离子电池拆卸后正极材料表面的 XRD图。
图 7是本发明实施例 3制做的锂离子电池膜表面的 XRD图。
图 8 是本发明实施例 2中不同隔膜所做的交流阻抗图谱。
具体实施方式
下面参照上述附图， 对本发明的具体实施方式进行详细说明。
包含 Li3P04的离子选择性传导膜的制备方法 （参见附图 1所示）：
可以包括以下步骤：
A. 将 Li3P04颗粒粉碎， 粒度达到 D5。= 0. 05〜50 Mra。 粉碎方式可包括球磨， 砂磨， 气流 粉碎磨， 超细粉碎磨等研磨方式；
B. 将 5〜25 \^%的聚偏氟乙烯和 5〜25 wt% 经过粉碎的磷酸锂， 分散于 55〜90 1%的有 机溶剂中， 均匀分散的方式包括球磨、 砂磨、 搅拌、 高速搅拌等；
C. 过滤去除未分散完全的物质和气泡；
D. 将所得的浆料体系， 通过流延机， 流延成膜， 烘干后厚度为 5〜50
E. 将所得薄膜， 按要求的规格尺寸裁切， 得到成品。
该膜制成工艺 ώ于采用了成熟的流延工艺， 膜的表观结构呈现为： 一侧面存在不光滑结 构， 另一侧面为较光滑致密结构。 不光滑一面可能使膜本身具有良好的与电解液的润湿性， 从而能够有效的降低膜面电阻。
实施例 1
包含 Li3P0J 离子选择性传导膜的制备：
将磷酸锂粉体球磨粉碎至 。 = 4 Mm。 将 52. 4 g聚偏氟乙烯-六氟丙烯 （PVDF- HFP) 溶解 于 149. 2 g丙酮与 200 g 1-甲基- 2-吡咯垸溺 （ P) 的混合溶剂中， 搅拌至聚偏氟乙烯完全 溶解， 然后加入 78. 6 g的磷酸锂粉体， 进一步研磨分散， 直至浆料均匀。 将所得浆料过滤除 泡， 使用薄膜流延机在表面光滑的载膜上流延成膜， 烘干后得到膜厚度为 20 μηι的致密膜。 致密薄膜与载膜接蝕的一面较为光滑致密， 另一面则为不光滑结构。 利用扫描电镜 SEM对隔 膜的表面进行形貌分析， 如附图 2所示， 从图中可以看出： 该面呈不光滑结构； 如附图 3所 示， 与载膜接蝕的这一面则较为光滑致密； 图 4为 Li3P04离子选择性传导膜的断面结构。
透气率测试：
测试方法： 通过透气率测试仪， 将膜夹在带有 1. 0 平方英尺的圆孔的标准垫片之间， 垫 片中心带有小孔允许气体流过， 在稳定的压力下， 测定一定体积的气体 （100 cc ) 流过特定 面积的试样所需的时间。 使用上述制得的包含 Li3P04的离子选择性传导膜做测试， 100 cc的 气体在 30分钟仍未能流过。 而用商品化的 Celgard 2320隔膜进行同样的测试， 100 cc的气 体在 350-450秒即可完全流过.
实施例 2
离子电导率测试：
将实施例 1制成的包含 1^^04的离子选择性传导膜与 Celgard 2320隔膜（厚度均为 20 Mm), 在电解液中 （LiPF6/EC- DEC, EC与 DEC的体积比为 1 : 1 ) 充分浸泡， 在 Ar气氛手套箱中将隔 膜夹在两个不锈钢片构成的阻塞电极之间， 在室温下， 利用电化学工作站进行交流阻抗测量。 测得数据如附图 8所示， 实线代表包含 Li3P0 离子选择性传导膜的交流阻抗变化曲线， 虚 线代表 Celgard 2320隔膜的交流阻抗变化曲线， 从中可以看出： 实施例 1制成的致密膜纯电 阻小于 Celgard 2320隔膜， 锂离子电导率更高。
实施例 3
包含 Li3P04的离子选择性传导膜的锂离子电池的制备：
正极制备： 按照比例， 将正极活性材料磷酸亚铁锂（LiFeP0,,87 Wt%、 导电炭黑 5 Wt%, 粘 合剂聚偏氟乙烯 PVDF 8 wt%) , 均匀分散于 N-甲基- 2-吡咯垸酮 ( MP) 溶液中， 制备成正极 的混合浆料， 并将浆料涂布于正极电流集流体铝箔上， 经过干燥辊压后得到正极极片。
负极制备： 按照比例， 负极活性材料 （炭粉 92 wt%、 导电炭黑 2 wt%, 粘合剂聚偏氟乙 烯 PVDF为 6 wt%) 均匀分散于 X-甲基- 2-吡咯烷 I (X P) 溶液中， 制备成负极的混合浆料， 并将浆料涂布于负极电流集流体铜箔上， 经过干燥辊压后得到负极极片。
电池制做： 将实施例 1 制成的致密膜做为隔膜， 并和上述制备的正极， 负极极片以叠片 方式形成标准钮扣式电池， 同时注入电解液 （浓度 1 mol/L的 LiPF6的碳酸亚乙酯 EC / 碳酸 甲乙酯 EMC = 1： 1的溶液）， 制成二次锂离子测试电池。
实施例 4
串联电池组里的单体电池由于容量不均衡造成单体电池受到反极或倒极充电工况放电的 模拟试验：
将在实施例 3中制做的锂离子电池以及使用 Celgard 2320隔膜制做成的锂离子电池进行 对比试验：
将两组使用不同隔膜制成的电池进行反极充电 （测试工作站的正极接电池负极， 而测试 工作站的负极接电池正极）。 结果发现， 反极充电后， 使用 Celgard 2320隔膜做成的锂离子 电池的正极材料上发现有大量金属铜析出的现象， 且电池发生短路而不能够正常工作。 将进 行反极充电的两组电池分别拆卸， 使用 Celgard 2320 隔膜制成的电池的正极材料表面进行 XRD测试， XRD图上有清楚的铜金属 XRD特征谱峰 （如附图 5所示）。 而使用实施例 3制备的 电池在反极充电测试后， 拆卸电池的正极材料表面上并没有金属铜析出现象， 在正极材料表 面进行 XRD测试没有出现铜金属的谱峰（附图 6所示）， 在隔膜上进行 XRD测试同样没有出现 铜金属的谱峰（如附图 7所示）， 而且同样制成的电池在反极充电后， 仍然可以继续进行充放 电循环。
实施例 5
电池过度放电的模拟试验
将实施例 3制做成的锂离子电池以及使用 Celgard 2320隔膜制做成的锂离子电池进行对 比试验：
将两组锂离子电池的放电电压从通常的 2. 5 V电压降至 1. 0 V和 0. 1 V， 进行放电电流为 0. 5 C的电池循环性能测试。 实施例 3制做成的锂离子电池经过 30个过度放电循环后仍能正 常工作， 而使用 Celgard 2320隔膜制做的锂离子电池在同样的过度放电循环 10次后即表现 出容量显著衰减现象， 基本无法进行正常充放电。
实施例 6
正极的活性材料表面直接流延致密膜的锂离子电池。
将磷酸锂粉体球磨粉碎至 D5。 = 4 μηι。 将 52. 4 g聚偏氟乙烯-六氟丙烯 （PVDF-HFP) 溶解 于 149. 2 g丙酮与 200 g 1-甲基- 2-吡咯烷溺 (NMP) 的混合溶剂中， 搅拌至聚偏氟乙烯完全 溶解， 然后加入 78. 6 g的磷酸锂粉体， 研磨分散， 直至制成均匀桨料。将所得浆料过滤除泡， 使用薄膜流延机在制做成的锂离子电池正极极片表面流延成膜， 烘干后得到致密正极电极极 片， 厚度为 20 Mm。 经过干燥辊压后即可与锂离子电池负极极片、 电解液制做成锂离子电池， 不再需要另外的隔膜。
实施例 7
负极的活性材料表面直接流延致密膜的锂离子电池。
按照实施例 6相同的工艺， 将所得浆料过滤除泡， 使用薄膜流延机在制做成的锂离子电 池负极极片表面流延成膜， 烘干后得到致密膜， 厚度为 20 。 经过干燥辊压后即可与锂离 子电池正极极片、 电解液制做成锂离子电池， 不再需要另外的隔膜。
实施例 8
Li3P04的离子选择性传导膜与多孔膜复合隔膜的制备：
将磷酸锂粉体球磨粉碎至 D5。 = 0. 3 Mm, D9。= 0. 6 Mm。 将 52. 4 g聚偏氟乙烯-六氟丙烯 ( PVDF-HFP) 溶解于 149. 2 g丙酮与 200 g 1_甲基 -2-吡咯烷溺 (NMP) 的混合溶剂中， 搅拌 至聚偏氟乙烯完全溶解， 然后加入 78. 6 g的磷酸锂粉体， 研磨分散， 直至制成均匀浆料。 将 所得浆料过滤除泡， 使用薄膜流延机， 严格控制刀头与载带间的间距， 在表面光滑的载膜上 流延成膜， 供干后得到薄膜厚度为 5 Wn。
将上述厚度 5 Mm 的薄膜与现有在锂离子电池中广泛使用的物理贯穿孔薄膜进行热压复 合， 控制压合温度 120 V , 压力 0. 35 kg/cm2， 得到包含 1^^04的离子选择性传导膜与多孔膜 直接复合的隔膜。
值得注意的是， 上述实施例中离子选择性传导层中的具有锂离子传导性的无机锂盐不限 于 Li3P04， 还可以是 Li3P04掺杂 B、 Si、 C. Al、 Ti或者 Zr中任意一种或者两种元素的化合 物。具有锂离子传导性的无机锂盐还可以是 Li2B407、 Li2Zr03、 Li2W0.,、 Li2Ti03、 Li2TeO Lija03, Li2Se04、 Li4SiO.;、 LiA102、 LiF、 LiB02、 Li3As04或者 a - LiAlSi206中的至少任何一种， 其原因 是它们和 Li3P04—样含有锂离子， 并且由于其晶体结构特征及掺杂后晶体缺陷能够进行锂离 子的交换和传导功能。
上述实施例中， 高分子聚合物除了 PVDF, 还包括 PAN、 或者 PVC中的至少一种。 但 是优选 PVDF- HFP， 因为 PVDF-HFP在电解液中具有很好的化学稳定性， 并且在锂离子电池电 极中也具有 PVDF作为粘合剂， 因此 PVDF聚合物系材料在锂离子电池中具有很好的化学相容 性。

Claims

1. 一种锂离子电池， 包括正极、 负极、 电解质体系， 其特征在于， 正极与负极之间还包 括离子选择性传导层， 该离子选择性传导层由高分子聚合物和具有锂离子传导性的无 机锂盐组成、 或者由具有锂离子传导性的无机锂盐组成， 所述的具有锂离子传导性的 无机锂盐包括 Li且 0X， 其中， m、 n的数值保证 LiJ„0x为电中性， M选自 B、 P、 Si、 Se、 Zr、 W、 Ti、 Te、 Ta、 Al或 As中的至少一种。
2. 根据权利要求 1所述的锂离子电池， 其特征在于， 所述的电解质体系为有机电解液体 系。
3. 根据权利要求 2所述的锂离子电池，其特征在于，所述的有机电解液是以 LiPF6、LiAsF6、 LiCIO,,或者 LiBF4中的至少一种为电解质， 以 EC、 PC、 EPC BC、 DME、 DMC EMC、 DEC 或者 DMF中的至少一种为溶剂配制成的有机溶液。
4. 根据权利要求 1所述的锂离子电池， 其特征在于， 所述负极包括铜、 镍、 铝、 不锈钢 合金中任意一种金属制成的电流集流体。
5. 根据权利要求 1所述的锂离子电池， 其特征在于， 所述负极上的活性材料包括含碳材 料或者钛酸锂。
6. 根据权利要求 1所述的锂离子电池， 其特征在于， 所述的离子选择性传导层的面积不 小于负极的面积。
7. 根据权利要求 1至 6任一所述的锂离子电池， 其特征在于， 所述的离子选择性传导层 是致密的。
8. 根据权利要求 7所述的锂离子电池， 其特征在于， 所述的离子选择性传导层为高分子 聚合物和具有锂离子传导性的无机锂盐共同制成的致密膜。
9. 根据权利要求 8所述的锂离子电池， 其特征在于， 所述的致密膜的膜两面之间没有同 时贯穿的物理贯穿孔。
10. 根据权利要求 9所述的锂离子电池， 其特征在于， 所述的具有锂离子传导性的无机锂 盐是分散在高分子聚合物中。
11. 根据权利要求 10所述的锂离子电池， 其特征在于， 所述的无机锂盐 Li O,中 M包括 元素 P。
12. 根据权利要求 11所述的锂离子电池， 其特征在于， 所述的 M还包括元素 B、 Si、 C, Al、 Ti或 Zr中的至少一种。
13. 根据权利要求 11所述的锂离子电池， 其特征在于， 所述的无机锂盐是 Li3P04。
14. 根据权利要求 10 所述的锂离子电池， 其特征在于， 所述的无机锂盐包括 LiA07、 Li2Zr03、 Liji03、 Li,SiO„ LiA102、 LiB02或者 a - LiAlSi206中的至少一种。
15. 根据权利要求 13所述的锂离子电池，其特征在于，所述的高分子聚合物包括 ΡΑΝ、ΡΜΜΛ、 PVDF、 PVC、 PVDF- HFP、 PVDF- CTFE、 PS或者 PES中的至少一种。
16. 根据权利要求 15所述的锂离子电池， 其特征在于， 所述的高分子聚合物包括 PVDF的 共聚物或者均聚物。
17. 根据权利要求 16所述的锂离子电池，其特征在于，所述的 PVDF的共聚物包括 PVDF-HFP。
18. 根据权利要求 16所述的锂离子电池， 其特征在于， 所述的 PVDF的均聚物由 PVDF组 成。
19. 根据权利要求 8至 18任一所述的锂离子电池， 其特征在于， 所述的致密膜为电池的隔 膜。
20. 根据权利要求 8至 18任一所述的锂离子电池， 其特征在于， 所述的致密膜为覆盖在电 池正、 负极表面的薄膜。
21. 根据权利要求 8至 18任一所述的锂离子电池， 其特征在于， 还包括一层多孔膜， 所述 的致密膜与多孔膜紧密贴合， 在多孔膜的至少一侧有贴合有所述的致密膜。
22. 根据权利要求 8至 18任一所述的锂离子电池， 其特征在于， 所述的致密膜的至少一面 为致密面。
23. 根据权利要求 7所述的锂离子电池， 其特征在于， 所述的离子选择性传导层为在覆盖 正极或负极材料的至少一个表面上的， 由具有锂离子传导性的无机锂盐的组成的薄层。
24. 根据权利要求 23所述的锂离子电池， 其特征在于， 所述的无机锂盐 中 M包括 元素 P。
25. 根据权利要求 24所述的锂离子电池， 其特征在于， 所述的 M还包括元素 B、 Si、 C、 Al、 Ti或 Zr中的至少一种。
26. 根据权利要求 24所述的锂离子电池， 其特征在于， 所述的无机锂盐是 Li3P(¾。
27. 根据权利要求 23 所述的锂离子电池， 其特征在于， 所述的无机锂盐包括 Li2B407、 Li2Zr03、 Li2Ti03、 Li4Si04、 LiA102、 LiB02或者 a - LiAlSi20e中的至少一种。
28. 根据权利要求 1至 6任一所述的锂离子电池， 其特征在于， 所述的无机锂盐！^^ 中 的 M包括元素 P。
29. 根据权利要求 28所述的锂离子电池， 其特征在于， 所述的 M还包括元素 B、 Si、 C.
Al、 Ti或 Zr中的至少一种。
30. 根据权利要求 28所述的锂离子电池， 其特征在于， 所述的无机锂盐是 Li3P(¾。
31. 根据权利要求 1 至 6 任一所述的锂离子电池， 其特征在于， 所述的无机锂盐包括 Li2B.A、 Li2ZrO:,、 Li2TiO:,、 Li4SiO,,、 LiA102、 LiB02或者 a - LiAlSiA中的至少一种。
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US9281540B2 (en) 2016-03-08
US20120251891A1 (en) 2012-10-04
CN102097647A (zh) 2011-06-15

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